Benzanthronylamino-thiophanthraquinone compounds



Patented Aug. 30, 1949 UNITED STATES PATENT OFFICE BENZANTHRONYLAMINO-THIOPHANTHRA- QUINONE COMPOUNDS Clarence F. Belcher, Bridgeton, N. J and Lorraine A. Mero, Wilmington, Del., assignors to E. I. du'Pont 'de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application November 15, 1947, Serial No. 786,335

wherein the thiophanthraquinonyl radical is attached to the -N in the or 8-position and X in each case is hydrogen or halogen.

It is an object of this invention to provide new and valuable compounds particularly suitable for use as dye intermediates containing the thiophanthraquinone nucleus attached to the EZ- group of the benzanthrone molecule through an amino linkage.

The compounds of the benzanthronylaminothiophanthraquinone series .of this invention may be prepared by condensing one mol of a 5- or 8-aminothiophanthraquinone with a monoor dihalogen benzanthrone (preferably the bromobenzanthrone) by the condensation methods ordinarily used in condensing aminoanthraquinone with halogen anthraquinone. As an alternative method, the 5- or 8-halogen thiophanthraquinone may be condensed with a Bz-l-aminobenzanthrone. Condensation may be carried-out under a wide variety of conditions as" totemperature and time, depending upon the reactants to be used. A temperature range of 180 215? C. usual- 1y gives most satisfactory results, although temperatures outside of this range may occasionally be employed. The time of the reaction depends upon the temperature chosen and the particular reactants. The condensations are preferably carried out in inert organic solvents such as aromatic hydrocarbons, and chlorinated or nitrated aromatic hydrocarbons. Condensation is eiiected by any of the usual methods employing acid binding agents such as inorganic or organic bases and catalysts such as copper salts.

The following examples are given to illustrate 2 the invention. The parts used are by weight, unless otherwise specified.

Example 1 A mixture of 128 parts of dry nitrobenzene, 16 parts of Bz-l-bromobenzanthrone, 12 parts of 5 amino-thiophanthraquinone, 6 parts of soda ash and 0.27 part of cuprous chloride are heated at 200-205 C. for eight hours, The charge is filtered at C., and the cake is reslurried in nitrobenzene at C. The violet-brown needle-like product is filtered off at 100 C., washed with hot nitrobenzene, alcohol, water and dried. The resulting 5-[Bz-l-benzanthronylaminol-thiophanthraqulnone may be represented by the formula:

Example 2 A mixture of 148 parts of nitrobenzene, 18.5 parts of 6,Bz-l-dibromobenzanthrone, 11 parts of 5-aminothiophanthraquinone, 6.5 parts of soda ash and 0.48 part of cuprous chloride is heated at i5 C. for eight hours. The charge is filtered at 80 C. and the cake is washed with nitrobenzene and reslurried in nitrobenzene at 140- 145 C. The violet-brown needle-like product, which is 5-[6-bromo-Bz-l-benzanthronylaminol-thiophanthraquinone, is filtered at 80 C., washed with nitrobenzene, alcohol and water. and dried. It may be represented by the formula:

Example 3 A mixture of 90 parts of nitrobenzene, 10.7 parts of Bz-l-bromobenzanthrone, 8 parts of B-aminothiophanthraquinone, 4.4 parts of soda with nitrobenzene, alcohol, water and dried, It

may be represented by the formula:

C&

In place of the bromoebenzanthrone employed in the above examples, the Bz-l-chlorobenzanthrone or the 6,Bz-1-dichlorobenzanthrone may be employed. Wherethedichloro compound is employed, the resulting chlorine-containing condensation productwill -be obtained. In a similar manner, the- 2-ehl0ro-5 aminothiophanthraquinoneor the- Z-chloro-8 aminothiophanthraquinone-may beemployed, inwhich case the resultingcondensation product contains chlorine in the -2position of th'e thiophanthraquinone radical.

The halogemcontainingv benzanthronylamino thiophantraquirrones maybe prepared in the mannerillustrated in the above examples. As illustrations may be'mentioned the condensation products of 2-chloro-5-aminothiophanthraquinone or 2-bromo-5-aminothiophanthraquinone with Bz-l-bromobenzanthrone' or Bz-l-chlorobenzanthrone; one mol of S-aminothiophanthraquinone with one mol of 6,Bz-1-dibromobenzanthrone or 6,132 ldichlorobenzanthrone; 2- chloro-5-aminothiophanthraquinoneor 2-bromo- 5-aminothiophanthraquinone with 6,132 1 dibromobenzanthrone or 6,Bz,-1-dichlorobenzanthrone; 2 chloro-8-aminothiophanthraquinone or 2-bromo-8-aminothiophanthraquinone with 6,Bz-1-dibromobenzanthrone, or 6,Bz-1-dichlorobenzanthrone.

The aminothiophanthraquinones employed'in the above examples, and their preparation, are more particularlydescribed in the co-pending application of Lee &- Weinmayr Serial No. 723,672 filed January 22,, 1947.

These new compoundsof the benzanthronylaminothiophanth'raqulnone series by treatmentv with alcoholic caustic alkalies give valuable new dyes which showa very marked and unexpected depth in shade and improved light fastness over analogous anthraquinonylamino benzanthrone compounds, as illustrated in co-pending application Serial No. 786,336 filed November 15, 1947, now Patent 2,480,110.

The 2-halogen-5-aminothiophanthraquinones employed as the starting materials in the preparation of theenew" compounds of this invention may be produced by the following process:

113 parts of 2-carbomethoxy-3-nitrobenzoic acid, 115partsof phosphorous pentachloride and 250 parts of dry benzene are mixed (rather carefully). The mixture is heated to 65 C. for 10 minutes to form the acid chloride, then cooled to 10 C., and 143 parts of anhydrous stannic chloride-areslowly added, followed ly a mixture of 89..parts"of 2-ch'loro-thiophene in 250 parts of benzene; Thesmixtureis then stirred at l0-15 C. for two hours and carefully poured into a mixture of 250 parts of ice water and 50 parts of concentrated hydrochloric acid. The benzene is removed by steam distillation, and the resulting aqueoussuspension is .cooledand :filtered. The filter cake'is Jslurried imatmixture' 0f'500 parts of water, 500 parts of 95% alcohol and 200 parts of.- sodium hydroxide solution for 18 hours to saponiiy, the methyl ester. The resulting slurry-is:diluted*with3000 parts of water, filtered, acidified'with hydrochloric acid and dried.

94=parts of the above product are dissolved in 6833parts'ofiwaterrcontaining 60 parts of 30% sodium:hydroxide,-..at room temperature. This solutiorris addedto a mixture of 583 parts of water, 147.,parts.o .iron powder and 63 parts of FeSCM-HHZO during the course of minutes at 95 C. The mixture is agitated for 10 minutes zit-95 C; then 35 gramsof sodium carbonate are slowly dusted in while cooling to 80 C. The hot solution! .is sfi-ltered, theefiltcrl 'oake. awashedawith suflicient hot: (90? C'.) watentocyielcl a 'clear'file trate, the combined! filtrates-a are; run slowly-into:

for 15 minutes; cooled to (3,, and at that temperature carefully diluted with 3000 partsof water to precipitate the 5-amino-2-ch1orothiophanthraquinone. The reaction mixture'is cooled to room temperature, filtered and washed acid-free. The

resulting wet filter cake is slurrie'd in 2000 parts of water containing; 100:.pa12t5 .of'sodium carbonate for 15 minutes at 60. ?-"C., Itiiscthen filtered,

washed alkali-rfreeeand dried: The product isv recrystallized irom 10-. parts: of orthodichloror benzene; toyieldthe-- substantially, pure 5- amino-2echlorothiophanthraquinone5 melting at 222-223'?- o.;

The 5 amino 2ebromothiophanthraquinone may be made in the same manner, starting with the z-bromothiophena We claim:

1. The benzanthronylaminoethiophanthraquinones ofthe..-formala::

in one of theposi-tions 5*and'8, and X in each case is an atom ofthe-group consisting 'of hydrogen and halogen;

The-resulting 2. The benzanthronylamino-thiophanthraqui- 4. The benzanthronylamino-thiophanth.raqulnone of the formula: none of the formula:

I H N 5 N S 10 l I I 0 o 3. The benzanthronylamino-thiophanthraqui- CLARENCE F. BELCHER. none of the formula: LORRAINE A. MERO.

REFERENCES CITED The following references are of record in the f file of this patent:

20 UNITED STATES PATENTS Number Name Date S 2,212,029 Lulek Aug. 20, 1940 

